Process for dyeing textiles made from acrylonitrile-containing polymers



PROCESS FOR DYEING TEXTILES MADE FROM ACRYLONITRILE-CONTAINING POLYMERS Archie G. Schoonover, South Charleston, Theophilus A. Feild, In, Charleston, and John H. Purse, South Charleston, W. Va., assignors to Union Carbide and Carbon Corporati n, a corporation of New York No Drawing. Application March 23, 1951, Serial No. 217,317

15 Claims. (CI. 8--55) This. invention relates to the dyeingwith water-soluble dyestuffs of the class of acid-type, direct-type and watersoluble acetate-type dyestuifs of textile articles formed from orcontaining filaments and fibers made of acrylonitrile-containing polymers. While the invention has especial utility for the dyeing of articles formedfrom polyacrylonitriles and from copolymers of acrylonitrile with vinyl halides, it is also useful for dyeing articles made from copolymers of acrylonitrile with a wide range of other polymerizable unsaturated compounds containing an olefinic double bond, such as acrylamide, alpha-methacrylamide, alpha-ethacrylamide, vinyl acetate, 2-vinylpyridine, and mixtures of such polymers and copolymers.

Processes already are known for dyeing fibers made from resins containing substantial proportions of acrylonitrile. inv the copolymer with dispersed dyes of. the type commonly used to color cellulose acetate rayon. Thus, resinous copolymers of. acrylonitrile and vinyl chloride containing around 40% of the acrylonitrile can be colored in a boiling dyebath with acetate-type dyestufis. Certain phthalic anhydride-, basicand acid-type dyestufis can be. applied to the same fibers by the use of dyebaths maintained under super-atmospheric pressure at temperatures above 100 C., or can be. applied at temperatures above 125 C. under atmospheric pressure in the presence of steam or moist heat.

It is well known that polyacrylonitrile, resins. are ex-v tremely resistant to, dyestuffs and that as the, acrylonitn'le content of copolymers of acrylonitrile' with such polymerizablecompounds as, vinyl halides increases,, the difficulty of dyeing increases. In the case ofcopolymersof acrylonitrile and vinyl chloride containing as much as %70% of the acrylonitr'ile, even the dispersed types of dyestuffs used for cellulose acetate, cannot. be applied on m y wi ut heuseof solvent. assis antsor sw lling agents for the copolymer.

finity for such copolymers. None of the methodspreviously known are entirely suitable. for the. dyeing of resin articles containing substantial amounts of acrylonitrile. with acid-type and neutral dyeing wool colors and withv direct cotton colors.

Among the more important objects of this invention;

nitn'le in the resinpolymer; thedyeing of; such fibers, and.

textile articles made from-or containing, the, same, in manner such tha he dyed. ar have f l bli t. color sha es nd. a e xcel ent wa h: nd. crockas nes It is a more specific object to dye fibers andtexl lSrrnadeof' synthetic resins havingsubstantial, proportions of acrylonitrile in the polymer with water-soluble dye-stuffs of hec-lasse snQ ncommer -ial v: 3-$':h.8ids. mord'antracid 31 neut al yeing, dyes. for wool,v the direct dyesitor: cotton, and the water-soluble acetate-type dyes.

p The. acid-type. and the. direct-type water-soluble dyestuffs, show little; or. no af- 2,743,991 Patented May 1, 1956 The invention is based in important part upon the discovery that finely divided copper, and compounds of copper capable of ionizing in aqueous acid and alkaline solutions, and more particularly those compounds wherein the copper ion is in the cuprous form, possess the remark- "ice able ability when present in an acid dyebath of causing certain acid dyeing wool colors, direct dyeing cotton colors and water-soluble acetate-type colors to become fixed on fibers and other textiles made from resins having substantial amounts up to of acrylonitrile in the; polymer, providing dyed articles having clear rich colors with excellent fastness to washing and crocking. The exhaustion of the dyebath is greatly improved. The best results are secured when the cuprous ions are formed in situ in the treating bath by reacting a. cupric compound and a reducing agent therefor in the presence of the article to be dyed, preferably before addition of the dyestufi to the bath. Eitheralkaline or acid conditions may be employed for the reduction, depending on the reducing agents used. While the mechanism involved in accomplishing these results is notv fully understood, it is thought that the cuprous ion forms a complex involving both the dyestufE and the fiber. The light fastness varies with the particular dyestuff used. Although cupric compounds have been found, to provide increases in dye pickup and fixation on these fibers, such compounds in the absence of reducing agents are not as effective as the. cuprous compounds.

As an indication of the specificity of this process for the, dyeing of textiles made of acrylonitrileecontaining polymers and copolymers, it has been found that the use of cuprous compounds and of metallic copper as practiced in this invention does not aidin the dyeing of cellulosic base fibers, or of fibers made from resinous copolymers of vinyl chloride and vinyl acetate with the acid and neutral dyeing acid colors not normally having affinity for such fibers. in instances Where the cuprous compounds areused in the dyeing with direct cotton colors of fibers made. from. acrylonitrile-vinyl chloride copolymersin admixture with cotton, the resin fibers commonly take most of the dye, showing the high dye afiinity created on the resin fibers by the process of the invention, Moreover, after-treatments of the dyed fibers In one preferred form of the invention for securing,

dyeings with deep .shades of color, fibers, yarns, or other textile articles, made from or containing a polyacrylonitrile, or a copolymer of acrylonitrile with a vinyl halide such as. vinyl chloride, are scoured in known man-v nor with an aqueous solution containing a suitable. detergent. Thev scoured article, after rinsing, is placed in an aqueous bath in the ratio by weight of one part of the textile to. from 10 to 100 parts of water containing from around 1% to 15%, based on the weight of the article, of a.v dyeing assistant capable. of swelling the acrylonitrilecontaining resin or of being dissolved thereby, and which usually is insoluble or only slightly soluble in water.

Many swelling or penetrating agents are useful in the. processfor securing dyeings having very deep shades of color. Particularly effective, are, derivatives of diphenyl and of benzylphenyl containing one or more hydroxy the form of their alkali metal salts in alkaline solution prior to acidification of the batth and addition of the copper compound and of the dyestutf. P-phenylphenol, which is a representative solvent assistant or penetrating agent, is highly etfective in proportions around 2%- 15% of the weight of the article being dyed. When dyeing stretched fibers, etc., too much of the solvent assistant causes excessive shrinkage of the article. When only medium or light shades of color are desired in the dyeings, a swelling or penetrating agent for the resin fiber is not required, and ordinarily is not used. Moreover, when dyeing textiles made from these acrylonitrile-com taining polymers and copolymers with water-soluble acetate-type dyestuifs, deep shades of color are readily secured by the process in the absence of an added swelling agent or dyeing assistant for the resin fiber.

For the best results, especially when seeking other than pastel shades, it is essential that the dyebath contain reduced copper ions. To secure this result there is added to the treating bath, either prior to or after acidification, a small amount, usually ranging from around 0.1% to 2% or more, based on the weight of the textile article, of copper or a cuprous compound which may be water-soluble or water-dispersible. Such compound can be added to the treating bath as such, or the cuprous compound can be formed in situ in the bath while alkaline by adding thereto a cupric compound and a suitable reducing agent for the latter, such as dextrose or glyoxaL- or while acid by adding thereto a cupric compound and a suitable reducing agent such as the metal formaldehydesulfoxylates, including the zinc and alkali metal salts. Metallic copper powder added to the treating bath provides the necessary copper ions in active form. Cuprous chloride, sulfite, and numerous other copper compounds are also useful in the process.

Best results are secured when using in the treating bath from 1% to 3% or more, based upon the weight of the textile to be dyed. of a dispersing and leveling agent, preferably one of the cationic or of the nonionic type. Highly effective for the purpose are the water-soluble cationic products of the condensation of ethylene oxide with an organic amine. Such a product now is being marketed under the trade name Peregal OK. Such products can be made by the process disclosed in United States Patent No. 2,214,352.

In one preferred form of the process the treating bath is prepared by mixing the desired amount of the swelling agent or dyeing assistant, usually around 2.25%, based on the dry weight of the textile material, with water in amount ranging from to 30 times the dry weight of the textile material. When a leveling agent is used, this is added to the bath in amounts generally around 2% of the weight of the textile. The dyeing assistant, when p-phenylphenol is used, conveniently can be added in the form of an aqueous solution of sodium p-phenylphenoxide, formed by reacting the former with approximately one-third its weight of a caustic alkali in boiling water.

The textile material is agitated in this bath for five minutes or more at room temperature, after which sufiicient formic acid, acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, or equivalent water-soluble organic or inorganic acid is added to convert the salt of phenylphenoxide to p-phenylphenol, when such salt is used, and to give the bath a pH of from around 2.0 to 7.0, and preferably between 2.0 and 4.5. The cuprous compound, or a mixture of a cupric compound such as cupric acetate and a sufiicient amount of a reducing agent to convert the copper to the cuprous form, then is added and uniformly distributed therein. The desired amount of dyestufi then is introduced and the bath brought to boiling. The dyeing usually is continued for from to 90 minutes at the boil. The dyed article is scoured at 140 F. in a dilute soap solution containing a detergent, rinsed with water, and then air dried at temperatures commonly around 160 F. Relustering may be done by heating the dry article at 240 F.250 F. with dry heat for a brief period.

In instances where a micronized p-phenylphenol or the like is used, or where no swelling agent or dyeing assistant is required as for example where water-soluble acetate-type dyestuffs are employed, it generally is not necessary to add acid to the treating bath since the copper compound employed is sufliciently acidic to impart to the dyebath a pH within the range between 2.0 and 7.0, and commonly around 4.5

It has been found that at dyeing temperatures below about 200 F. almost no dye fixation on the textile is securable unless a solvent assistant or swelling agent is used in the dyebath. On the other hand, in the presence of such a swelling agent good dyeings are secured at temperatures as low as 175 F. on textiles made from these resins. The amount of copper or copper compound employed depends to a considerable degree upon the depth of color desired. For full shades such as black, a dyebath containing 0.64% of the copper ion (corresponding to 2% of copper acetate), based on the weight of the fabric, appears to be an optimum, whereas for light color shades as little as 0.08% of copper ion, corresponding to 0.25% of cupric acetate, in the dyebath gave optimum results.

The following examples serve to illustrate the invem tion. In the examples all parts are given in terms of weight, and all percentages are based upon the dry weight of the textile material being treated, unless otherwise specified. During the dyeings, each dyebath had a pH within the range from 2.0 to 7.0.

EXAMPLE 1 A quantity of yarn spun from a resinous copolymer of acrylonitrile and vinyl chloride containing 40% acrylonitrile in the polymer and having a specific viscosity at 20 C. of 0.26 was scoured in an aqueous solution of a detergent, and then was treated for 10 minutes in an aqueous bath at room temperature, the weight ratio of dyebath to dry yarn being 30:1. The treating bath was prepared by mixing with the water 3% of sodium pphenylphenoxide, 3% of acetic acid, 1% of cupric sulfate and 0.4% of zinc formaldehydesulfoxylate.

Then 5% of an acid dyestutf Cloth Red G (C. I. 249) in solution in water were added and the bath temperature was slowly raised to 212 F. and held there for minutes. The dyed fabric was scoured, and then dried at 248 F. for 15 minutes. It had an excellent, uniform full shade with good washand crock-fastness.

EXAMPLE 2 A yarn spun from a copolymer of acrylonitrile and vinyl chloride having an acrylonitrile content of 40% and a specific viscosity at 20 C. of 0.26 was scoured and then was treated at room temperature for 10 minutes in 30 times its weight of an aqueous bath containing 3.0% of a cationic condensation product of ethylene oxide and an organic amine being marketed under the trade name Peregal OK, 3.0% of sodium p-phenylphenoxide (which was made prior to addition to the bath by reacting 2.25% p-phenylphenol with 0.75% sodium hydroxide in a small amount of boiling water), and cuprous acetate (made by reducing 1% cupric acetate with 1% dextrose prior to addition to the bath by boiling for a brief period in the sodium p-phenylphenoxide solution). Thereafter, 4.5% of glacial acetic acid and 2% of Xylene Milling Navy 4B Conc., C. I. No. 304, an acid-type dyestutf, were added, the bath heated to boiling, and dyeing at this temperature continued for 90 minutes. The dyed yarn was scoured, and dried at 248 F. for 15 minutes. The dyed yarn had an excellent uniform full shade with good washand crock-fastness.

EXAMPLE 3 Y The following examples illustrate the great improvement over prior processes in color intensity of the dyed arti e. when. am ade, ree! ee f 'eni rile-v le qhlqr isle copolymer resins are dyed by theproqess of thisfinyention, but; omitting a, swelling agent, and/or omitting a copper compound.

In s xa spqr i es i h Y ms de ib in ample 2 were dyed, respectively, with two acid-type dyes and with one direct-type dye under the conditions described in Example 2 with the exception that of the dyestufis were used, and the components of the bath were varied. After the dyed yarns were scoured and dried, the color depths, of thedried yarnswere measured with a photovolt photoelectric reflection meter, model No. 600, using the filteddesignated. The greater the color depth of the dyed yarns the lower is the light reflectance reading on this meter for these dyes, In Table A, presenting the light reflectance readings, the values in column A are those secured from dyeings conducted without the aid of either a swelling agent or of a copper compound; those in column B were secured from dyeings conducted with the aid of a swelling agent but without the copper compound; those in column C were secured from dyeings conducted in the absence of a swelling agent but in the. presence of a cuprous compound; and those in column D were secured from dyeings conducted according to Example 2 in the presence of both a swelling agent, p-phenylphenol, and a cuprous compound, the acetate.

N orE.-Dyestufi 1 was Xylene Milling Black 23; Color Index 304; Dyestutf 2 was Brilliant Alizarine Light Red B; and Dystuti 3 was Pontamine Fast Red BBL Cone. 125%, Color Index 278.

EXAMPLE. 4

Following the procedure described in ExampleZ fabrics knitted, respectively, from yarns made ofcotton, of viscose rayon, of cellulose acetate and of a copolyrner of vinyl chloride and vinyl acetate having 90% of the chloride in the copolymer were dyed with each of the following dyestufis: (1) Xylene Milling Black 2B, Color Index No. 304 yp r li nt a a L htzR idtype) and (3 Bontamine Fast Red 8 BL Conc. 125%, Color Index No. 278 (a direct-type dyestufi).

In each dyeing the affinity: of the. fiber for the dyestufi was very low, and in the case of the direct dyestufi, the shade on the cotton and the viscose rayon was below the shade obtained in a normal direct dyeing procedure for these fibers.

X M E5 A knitted fabric made from yarn spun from a resinouscoplyomer of acrylonitrile and vinyl chloride having an acrylonitrile content of 67% and a specific viscosityat C. of 0.28 was scoured and then treated at room temperature in an aqueous bath in the proportion of one part of the fabric to parts of the aqueous bath containing sodium p-phenylphenoxide (formed by reacting 12% of p-phenylphenol in water with 4% of sodium hydroxide). Three per cent of Peregal OK then were added to the bath and the temperature thereof raised to the boiling point, after which 2% of finely divided copper powder were added together with sutficient formic acid to reduce the pH to 3. Cuprous ions were released. Then 5% of- Xylene Milling Black 25 (Color Index No. 304) were added to the bath and the dyeing continued at the boil for 90 minutes. The dyed fabric was scoured, and then was dried at 248 F. for 15 minutes. excellentwaslrand crock-fast dyeing was secured. The dyestutf exhausted completely from the bathand gave thefabric a full blacl; shade.

6 EX M LE. v

A; knitted tabric made of a; commercially, available polyacrylonitrile fiber being marketed under the trade name Qrlon and said to contain over and up to of acrylonitrile in the polymer, and having a nitrogen content of 24.5 was dyed in the manner described in Example 5, excepting that 5% of an acid-type dyestuff Xylene. Millingv Blue BL, Color Index No. 833, were used. The dyed fabric had amedium shade; and the washand crock-fastness were good. In a similar dyeing wherein the copper compound was omitted, only a very faint pastel shade was obtained.

EXA PLE 7 The data in Table B illustrate the highly specific nature of the action of reduced copper and cuprous compounds upon the dyeings of textiles made from or containing polyacrylonitrile and copolymers of acrylonitrile and vinyl chloride.

Knitted fabric spun from yarns of an acrylonitrilevinyl chloride copolymer resin containing 40% of acrylonitrile in the copolymer and having a specific viscosity at 20 C. of 0.26 was dyed in the manner described in Example 2, using in the respective dyeings 5% of a corresponding one of the three dyestufls recited in Example 4, with the exception that in certain dyeings 1% of various other metals and metal compounds were substituted for the cupric acetate of Example 2;. When such other metals or metal compounds were used they were added directly to the treating bath without any prior attempt to change the valence of the metallic ion. The color depths of the dyed fabrics, after scouring and drying, were measured with a photovolt photoelectric reflection meter by deter-- mining the light reflectance of the dyed examples. The undyed fabric gave a value of 76.0% reflection when measured with a red filter and of 60% when measured with a tristirnulus green filter. Lower reflectance values indicate greater color depths. The results are given in Table B.

TABLE B Light Reflectance, Percent Metal or Metallic Compound Dyestuff 2 of Ex. 4

Dyestuti of Ex. 4

Metallic Zinc. Metallic Copper..

Calcium, Oxide Chromium Oxide..-

wwmzew 9 5 5 5 7 crows moms: \lquo summo- Manganous Sulfate. Cuprie Sulfate Aluminum Acetate... Chromium Acetate Magnesium Acetate Cupric Acetate l Mercurous Cloride Stannous Chloride. Zinc Chloride Cuprous Chloride.

Sodium Dichromate 1 as h d to the ban MM E. 3

bath to yarn weight ratio of 30:1. The bath was prepared by mixing with water 3% of Peregal OK, sodium p-phenylphenoxide in amount equivalent to 9% of pphenylphenol, and 0.5% of cuprous sulfite. The yarn was agitated in this bath at room temperature, and 9% of glacial 'acetic acid then were added and agitation continued. After 10 minutes of the dyestutf were added to the bath, the temperature thereof was raised to 176 F., and this temperature was held for 90 minutes. The dyed yarn had a good deep shade of color. A similar dyeing made in the absence of the copper compound gave a very light shade.

EXAMPLE 9 A spun yarn made from a copolymer of acrylonitrile and vinyl chloride having an acrylonitrile content of 40% and a specific viscosity at 20 C. of 0.25 was scoured and then treated at room temperature for a short time in an aqueous bath containing 2% of Peregal OK, 1% of cupric acetate, 0.5 of zinc formaldehydesulfoxylate and 0.5% of sulfuric acid (100%), and having a pH of 3.5. Then 4% of Xylene Milling Blue BL were added and the temperature of the dyebath was raised to a boil and dyeing at this temperature was continued for 90 minutes. The ratio of dyebath to yarn was 30:1. The dyed yarn was scoured, and then dried at 248 F. for 15 minutes. An excellent uniform shade of color was obtained, and the dyed yarn had good washand crock-fastness.

EXAMPLE A spun yarn formed from a copolymer of acrylonitrile and acrylamide having 86% of acrylonitrile in the copolymer and a specific viscosity at 20 C. of 0.4 was scoured, and then treated in an aqueous dyebath, the

weight ratio of bath to yarn being 30:1. The scoured yarn was immersed in water to which had been added 3% of sodium p-phenylphenoxide, 2% of Peregal OK, 1% of cupric sulfate, 0.5% of zinc formaldehydesulfoxylate and 3% of acetic acid (99%). After a short time 4% of Xylene Milling Blue BL, an acid dyestufi (Color Index No. 833) were added and the bath temperature raised slowly to a boil and maintained for 90 minutes.

The dyed yarn then was dried at 248 F. for minutes. An excellent uniform full shade was obtained which had good wash fastness. When the same yarn was dyed under the same conditions excepting for the omission of the cuprous ions and the p-phenylphenoxide, a very low pastel shade was produced.

EXAMPLE 1] A woven fabric was made from a yarn spun from a resinous copolymer of acrylonitrile and vinyl acetate in admixture with poly-2-vinylpyridine, the mixture containing about 90% of acrylonitrile, around 5% of vinyl acetate and around 5% of poly-2-vinylpyridine. The fabric was scoured and then treated at room temperature in an aqueous bath, the weight ratio of bath to dry fabric being 100:1. Then, successively, there were added to the treating bath 2% of Peregal OK; sodium p-phenylphenoxide formed by reacting 10% of paraphenylphenol with 3.3% of sodium hydroxide in water; 10% of glacial acetic acid; 2% of cupric sulfate and 1% of zinc formaldehydesulfoxylate. Then 5% of Xylene Milling Blue BL were added to the dyebath and the temperature was raised to 2l0212 F. and dyeing continued for 90 minutes. The dyed fabric was scoured and then dried at 248 F. for minutes. The fabric was dyed a deep blue shade having excellent wash-fastness. Almost complete exhaustion of the'dyestuii was secured.

Similar results were secured when substituting for the aforesaid dyestutf an equal amount of Pontamine Fast Red SBL Conc. 125%. The fabric was dyed a full deep red color; and the dyed fabric had excellent wash-fastness.

In contrast therewith, similar dyeings of the fabric with these dyestuffs but omitting the copper compound and the reducing agent merely tinted the fabric.

EXAMPLE 13 Skeins of yarn spun from a mixture of polyacrylonitrile and poly-Z-vinylpyridine and containing about 92% of acrylonitrile, about 5% of 2-vinylpyridine and around 1.6% of titanium dioxide were dyed in the manner described in Example 12 with the two dyestuffs named in that example. The resultant yarns were dyed, respectively, a deep blue shade and a full deep red shade. The dyeings had excellent wash-fastness. Almost complete exhaustion of the dyestuffs from the dyebaths was secured.

In contrast therewith, similar dyeings of the skeins with these dyestuffs but omitting the copper compound and the reducing agent merely tinted the skeins.

Examples 14 to 18 inclusive, exemplify the dyeing of textiles made from these resinous polyacrylonitriles and acrylonitrile-containing copolymers with water-soluble acetate-type dyestutfs. No softening agent for the resin nor added acid was required in the dyebath. Excellent dyed products were secured.

EXAMPLE 14 A quantity of the woven fabric described in Example 12 was scoured and then was treated at room temperature in an aqueous bath, the weight ratio of bath to dry fabric being 60:1. Then, successively there were added to the treating bath 1% of a wetting agent being marketed under the trade name Tergitol-7, 2% of cupric sulfate and 1% of zinc formaldehyde-sulfoxylate. Then 5% of a water-soluble acetate-type dyestutf being marketed under the trade name Solacet Fast Scarlet B-125" dissolved in water were added and the temperature of the dyebath raised to 210212 F. and the dyeing continued at that temperature for minutes. The dyebath had a pH of about 4.5. The dyed fabric then was scoured and was dried for 20 minutes at 245 F. The resultant fabric was dyed a deep scarlet shade having excellent wash-fastness. Almost complete exhaustion of the dyestuff from the bath was realized.

In contrast therewith, dyeings of the same fabric under the same conditions without cuprous ions present in the dyebath gave only a very light shade on the fabric.

EXAMPLE 15 EXAMPLE 16 Following the procedure and using the treating agents described in Example 14, staple fibers made from a resinous copolymer containing 92% of acrylonitrile, 5% of polyvinylpyridine and 1% to 2% of titanium dioxide were dyed a deep scarlet shade having excellent washfastness.

EXAMPLE 17 A quantity of continuous filament yarn sold commerc'ially as acrylic fiber under the trade name Orlon, having a nitrogen content of 24.5%, and said to contain over 85% of acrylonitrile, was dyed with 5% of Solacet Fast Scarlet B- dyestuff under the conditions de dried; at medium. s adeo a let.- n. r t herewi h. s mi yeings. f? e; same yarn the b n f he. pp r-- compound from the dyebath gave only a very faint. tint.

EXAMPLE 18 A knitted fabric made from a yarn formed from a vinyl chloride-acrylonitrile copolymer resin containing 40%, of acrylonitrile in the polymer was dyed; with of Solacet Fast Scarlet B125 dyestufl under theconditions described in Example, 14. The resulting fabric was dyed a,deep,sc,arlet shade having excellent wash-fastness. Almost complete exhaustion of the dyebath wassecured.

In contrast .therewithLsimilar dyeing of the same fabric under the same conditions but omitting the copper: compound gave .the fabric a light scarletshade. 4

Amongthe many dyestuffs found particularly suitable for use in the process are the following:

Acid-type dyestufis- Tradenarne: Color IndexNo. XyleneMillingBlue BL 833.. Vitrolan Orange R. Conc Pr. 14 6- Xylene; Milling Yellow: P Xylene Milling Yellow 2GP XyleneFast Red' 2GP Xylene Light RubineZGS Calcoid Neutral Brown RS Anthralan Red BA-CF Pr; 210, Chromaven Milling Orange G C0nc 274 Aliz eht Brown BL--- Alizarine-Light Green GSN- Aliz arine Light Gray RLL AlizarineLight-Red R Alizarine Sky Blue BSCF 1088 Alizarine Cyanine Green GHN-CF 1078 Brilliant Alizarine Light Red 4B Sulfonine Red G 430 Calcochrome Alizarine Gray 2BLS- Pr. Z06 Xylene; Fast Rubine 3 GP P11 4 12 Amacid; Red 3B Conc 208- Sulfonine; Orange, GS Y.'.. Br. 15:1, Sulfonine Yellow 2G 6 42v Cloth Red G 249 Croceine; Scarlet; MOO 252; Anthraquinone. Violet R 1080,

Supramine, Yellow 3GLA-'CF.' Pr. 474 Gal id M l gk R C0 215 Direct-type dyestufi Tradename: Color- Index No.

Calcomine Brilliant Yellow Conc 365 Fastusol Brown LBR Fastusol Red 4BA 278- Calcodur Yellow BL Conc 81-4 Qalcodur Yellow NN 8 l4 v Water-soluble acetate-type dyestufls Trade name: Color Index No.

Solacet Fast Violet RS Solacet Fast Yellow GS Solacet Fast Scarlet B-125 Solacet Fast Green 2GS Solacet Fast Blue 2BS Solacet Fast Orange 2GKS Solacet, Fast Red 5BGS Variations in the order of the procedure of adding to,

i It is not-essential that the cuprous compoundbe added, to the bathprior to the addition of the dyestuif; On the contrary, the dyeing can be begun in the absence of a copper; compound, and all'ofi the cuprous compoundcan befadded tothe dyebath at one time or in successive amounts after-the dyeing of the article has been initiated.

The specific viscosities of the resins referred to,herein were determinedat 20 C using an Ostwald viscosimeter in accordance with the formula:

Specific viscosity:

Viscosityof a solution of 0.1 gram of'the resin in 50 cc. of solvent Viscosity of the solvent In determining these specific viscosities, cyclohexanone was used with the resins of Examples 1 to 3 and 7 to 9; anddirnethylformamide was used, with the resins of Examples 5; 6, 10 and 11. The specific viscosity of the resin is a direct function of its average molecular weight.

This application is a. continuation-impart of our pending. application, Serial No. 172,194, filed July 5, 1950, now abandoned.

The invention is susceptible of modification within the scope of the appended claims.

We claim:

1. Brocess for dyeing textile articles made from polyacrylonitriles and copolymers of acrylonitrile with another singly unsaturated compound containing an olefinic double bond, which comprises treating such an article with an aqueous solution containing a small amount of a compound yielding cuprous ions and a water-soluble dyestufi" selected from, the, class consisting of the acidtype and the direct-type dyestuffs and heating the article in said solution. at a temperature of at least F. for at least 15 minutes, said dye-containing solution having a pH between around. 2.0 and 7.0.

' 2. Process for dyeing textile articles made from polyacry lonitr iles and copolymers of, acrylonitrile with an other singly unsaturated polymerizable compound containing. an. olefinic double bond, which comprises treating such an article With an aqueous solution containing at least 0.1% of a compound yielding cuprous ions and a water-soluble dyestuff selected from the class consisting ofthe-acid-type andtlie direct-type dyestuffs and heating thearticle in said solution at a temperature of at least 200 F. for at least 15 minutes, said dye-containing solution having a pH between around 2.0 and around 7.0.

3. Process; for dyeing textile articles madefrom resinous. copolymersof acrylonitrile with another singly unsaturated polymerizable compound: containing an olefinic double bond, which comprises treating such an article with anaqueous solution containing at least 0.1% of a cuprous compound and adding to the solution a watersolubledyestutf selected from the class consisting of the acid=type and the direct-type dyestuffs and heating the article in saidsolution at a temperature of at least 175 P for at least 15 minutes, and at some stage prior to the addition of the dyestufi'intimatelymixing with such solution containingthe article a water-soluble acid in amount sufiicient to, impart to the solution a pH of between r un ,-0 a ,0,-

4, Process for dyeing textile articles made from resinus; pe ymers. ec d r m h a s Consisting of P 3: a crylonitrilesand the copolymers of acrylonitrile with vinyl chloride, with acrylamide, with the alpha-alkyl substituted acrylamides, with vinyl acetate,and with 2-vinylpyridine, respectively,- which comprises treating such an article with an aqueous solution containing at least 0.1% of a cuprous compound, and adding to the solution a water-soluble dyestutf selected from the class consisting of the acid-type. and the direct-type dyestuifs and heating the article in said solution at a temperature of at least,

.75. Bibi-".- at e s .5,. m nutes. an a Stage Prior *2- h aq f n of. he new, a m t l mix h such solution containing the article a water-soluble acid in amount sufiicient to impart to .the solution a pH of between around 2.0 and 7.0.

5. Process for dyeing textile articles madefrom resinous polymers selected from the class consisting of polyacrylonitriles and the copolymers of acrylonitrile with vinyl chloride, with acrylamide, with the alpha-alkyl substituted acrylamides, with vinyl acetate, and with 2-vinylpyridine, respectively, which comprises treating such an article with an aqueous solution containing a small amount of a cuprous compound and a swelling agent for the resin, and thereafter adding to the solution a watersoluble dyestufi selected from the class consisting of the acid-type and the direct-type dyestufiFs and heating the article in said dye-containing solution at a temperature of at least 175 F. for at least 15 minutes and, at some stage prior to the addition of the dyestult, introducing into the solution an acid, in amount sufiicient to provide the aqueous solution with a pH between around 2.0 and around 7.0. 6. Process for dyeing textile articles made from resinous polymers selected from the class consisting of polyacrylonitriles and the copolymers of acrylonitrile with vinyl chloride, with acrylamide, with the alpha-alkyl substituted acrylamides, with vinyl acetate, and with 2-vinylpyridine, respectively, which comprises treating such an article for at least 5 minutes with an aqueous solution containing cuprous ions and a compound selected from the class consisting of the phenylphenols, the henzylphenols and the biphenols, said solution also containing a water-soluble acid in amount sufficient to give the aqueous solution a pH between around 2.0 and around 7.0, and thereafter adding to such solution a water-soluble dyestutt selected from the class consisting of the acid-type and the direct type dyestufis and dyeing the article therein at a temperature of at least 175 F. for at least minutes.

7. Process for dyeing textile articles made from resinous polymers selected from the class consisting of polyacrylonitriles and the copolymers of acrylonitrile with vinyl chloride, with acrylamide, with the alpha-alkyl substituted acrylamides, with vinyl acetate, and with 2-vinylpyridine, respectively, which comprises treating such an article with an aqueous solution containing p-phenylphenol, cuprous ions, and a lower fatty acid having up to three carbon atoms in the molecule in amount sufficient to give the aqueous solution a pH between around 2.0 and around 7.0, and thereafter adding to the treating solution in contact with said article of water-soluble dyestufi selected from the class consisting of the acid-type and the direct-type dyestutls, and dyeing the article therein at a temperature of at least 175 F. for at least 15 minutes.

8. Process for dyeing textile articles made from resinous polymers selected from the class consisting of polyacrylonitriles and the copolymers of arcylonitrile with vinyl chloride, with acrylamide, with the alpha-alkyl substituted acrylamides, with vinyl acetate, and with 2-vinylpyridine, respectively, which comprises treating such an article for at least 5 minutes with an aqueous solution containing p-phenylphenol, a dispersing and leveling agent of the cationic type, a cupric compound and a compound adapted to reduce the latter to the cuprous form, and thereafter adding to the solution a water-soluble dyestutf selected from the class consisting of the acid-type and the direct-type dyestuffs and dyeing the article therein at a temperature of at least 175 F. for at least 15 minutes, and at some stage during the treatment of the article prior to the addition of the dyestutf adding to the solution a water-soluble acid in amount sutficient to give such solution a pH between around 2.0 and around 7.0.

9. Process for dyeing textile articles made from resinous polymers selected from the class consisting of polyacrylonitriles and the copolymers of acrylonitrile with vinyl chloride, with acrylamide, with the alpha-alkyl substituted acrylamides,

with vinyl acetate, and with Z-vi- 12 nylpyridine, respectively, article for at least 5 minutes with an aqueous solution containing p-phenylphenol, a cupric compound, a metal formaldehydesulfoxylate and a water-soluble acid, said acid being present in amount sufiicient to give said aqueous solution a pH between around 2.0 and around 7.0, and thereafter adding to such solution containing such article a water-soluble dyestufi selected from the class consisting of the acid-type and the direct-type dye stuffs and heating such solution at a temperature of at 'least F. for at least 15 minutes.

10. Process for dyeing textile articles made from resinous polymers selected from the class consisting of polyacrylonitriles and the copolymers of acrylonitrile with vinyl chloride, with acrylamide, with the alpha-alkyl substituted acrylamides, with vinyl acetate, and with 2-vinylpyridine, respectively, article for at least 5 minutes with an aqueous alkaline solution containing a compound of the class consisting of the phenylphenols, the benzylphenols and the biphenols,

a dispersing and leveling agent of the cationic type, a

cupric compound, and a reducing agent for such cupric compound, and thereafter adding to such solution a water-soluble dyestufiE selected from the class consisting of the acid-type and the direct-type dyestuffs, and heating the solution at a temperature of at least 175 F. for at least 15 minutes, and at some stage prior to the addition of said dyestuff adding to such solution a watersoluble acid in amount suflicient to give such solution a pH between around 2.0 and around 7.0.

- 11. Process for dyeing textile articles made from resinous polymers selected from the class consisting of polyacrylonitriles and the copolymers of acrylonitrile with vinylchloride, with acrylamide, with the alpha-alkyl substituted acrylamides, with vinyl acetate, and with 2-vinylpyridine, respectively, which comprises treating such an article for at least 5 minutes with an aqueous solution containing between 1% and 15% of a compound of the class consisting of the phenylphenols, the benzylphenols and the biphenols, at least 1% of a dispersing andleveling agent of the cationic type, between 0.1% and 3.0% of a cupric compound, between 0.1% and 2.0% of a metal formaldehydesulfoxylate, and sufficient of a watersoluble acid to give such solution a pH between 2.0 and 7.0, and thereafter adding to such solution a water-soluble dyestuff selected from the class consisting of the acidtype and the direct-type dyestuffs, and heating the solution at a temperature of at least 175 F. for at least 15 minutes.

- 12. Process for dyeing textile articles made from resinous polymers selected from the class consisting of poly acrylonitriles and the copolymers of acrylonitrile with vinyl chloride, with acrylamide, with the alpha-allay] substituted acrylamides, with vinyl acetate, and with 2-vinylpyridine, respectively, which comprises treating such an article for at least 5 minutes with an aqueous solution containing a dispersing and leveling agent of the cationic type, at least 0.1%, based upon the weight of the article,

of a cupric compound, and a reducing agent for such cupric compound, and thereafter adding to the solution a water-soluble dyestuff selected from the class consisting of the acid-type and the direct-type dyestuffs and heating the article in such aqueous solution at a temperature of at least 200 F. for at least 15 minutes, and at some stage prior to the addition of the dyestuff adjusting the solution to a pH of between 2.0 and 7.0 by the addition thereto of a water-soluble acid. i

' 13. Process for dyeing textile articles made from polyacrylonitriles and copolymers of acrylonitrile with at least oneother unsaturated compound containing a single olefinic double bond, which comprises treating such an article with an aqueous solution, a small amount of a water-soluble dyestutf selected from the class consisting of the acid-type and the direct-type: dyestuffs, and heating the article in the dye-containing which comprises treating such an which comprises treating such an adding to such solution;

solution at a temperature of at least 175 F. for at least 15 minutes, said dye-containing solution having a pH between around 2.0 and 7.0, and at some stage during contact of the article with said aqueous solution adding thereto a small amount of a compound yielding cuprous ions.

14. Process for dyeing textile articles made from polyacrylonitriles and from copolymers of acrylonitrile with at least one other sin'gly unsaturated organic compound containing a single olefinic double bond, which comprises treating such an article with an aqueous solution containing a small amount of a compound yielding cuprous ions and a small amount of a water-soluble dyestuif selected from the class consisting of the acid-type and the directtype dyestuffs, and heating the article in said dye-containing solution at a temperature of at least 175 F. for at least 15 minutes.

15. Process for dyeing textile articles made from polyacrylonitriles and copolymers of acrylonitrile with at least one other polymerizable compound containing a single olefinic double bond, which comprises treating such an article with an aqueous solution having a pH within the range from 2.0 to 7.0, and containing a water-soluble dyestufi selected from the class consisting of the acid-type and the direct-type dyestuifs While adding to said aqueous solution successive amounts of a compound yielding cuprous ions, and while heating the article in the dye-containing solution at a temperature of at least 200 F. for at least 15 minutes.

References Cited in the file of this patent 

1. PROCESS FOR DYEING TEXTILE ARTICLES MADE FROM POLYACRYLONITRILES AND COPOLYMERS OF ACRYLONITRILE WITH ANOTHER SINGLY UNSATURATED COMPOUND CONTAINING AN OLEFINIC DOUBLE BOND, WHICH COMPRISES TREATING SUCH AN ARTICLE WITH AN AQUEOUS SOLUTION CONTAINIG A SMALL AMOUNT OF A COMPOUND YIELDING CUPROUS IONS AND A WATER-SOLUBLE DYESTUFF SELECTED FROM THE CLASS CONSISTING OF THE ACIDTYPE AND THE DIRECT-TYPE DYESTUFF AND HEATING THE ARTICLE IN SAID SOLUTION AT A TEMPERATURE OF AT LEAST 175* F. FOR AT LEAST 15 MINUTES, SAID DYE-CONTAINING SOLUTION HAVING A PH BETWEEN AROUND 2.0 AND 7.0. 